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Exchanges of energy and mass between the surrounding air and plant surfaces occur below, within, and above a forest's vegetative canopy. The canopy also can lead to vertical gradients in light, trace gases, oxidant availability, turbulent mixing, and properties and concentrations of organic aerosols (OA). In this study, a high-resolution time-of-flight aerosol mass spectrometer is used to measure non-refractory submicron aerosol composition and concentration above (30 m) and below (6 m) a forest canopy in a mixed deciduous forest at the Program for Research on Oxidants: Photochemistry, Emissions, and Transport tower in northern Michigan during the summer of 2016. Three OA factors are resolved using positive matrix factorization: more-oxidized oxygenated organic aerosol (MO-OOA), isoprene-epoxydiol-derived organic aerosol (IEPOX-OA), and 91Fac (a factor characterized with a distinct fragment ion at m/z 91) from both the above- and below-canopy inlets. MO-OOA was most strongly associated with long-range transport from more polluted regions to the south, while IEPOX-OA and 91Fac were associated with shorter-range transport and local oxidation chemistry. Overall vertical similarity in aerosol composition, degrees of oxidation, and diurnal profiles between the two inlets was observed throughout the campaign, which implies that rapid in-canopy transport of aerosols is efficient enough to cause relatively consistent vertical distributions of aerosols at this scale. However, four distinct vertical gradient episodes are identified for OA, with vertical concentration differences (above-canopy minus below-canopy concentrations) in total OA of up to 0.8 μg/m3. The magnitude of these differences correlated with concurrent vertical differences in either sulfate aerosol or ozone. These differences are likely driven by a combination of long-range transport mechanisms, canopy-scale mixing and local chemistry. These results emphasize the importance of including vertical and horizontal transport mechanisms when interpreting trace gas and aerosol data in forested environments.

Gas-phase biogenic volatile organic compounds (BVOCs) are oxidized in the troposphere to produce secondary pollutants such as ozone (O3), organic nitrates (RONO2), and secondary organic aerosol (SOA). The nitrate radical (NO3) is especially reactive towards isoprene and monoterpenes such as α-pinene. A zero-dimensional model has been used to investigate differences in oxidation and SOA production from these two BVOCs, especially with respect to hydroxyl radical (OH) and NO3, above and below a forest canopy in rural Michigan using local data and data from a monitoring site in Detroit. In all modeled scenarios, NO3 concentrations are relatively small (0.5–3 pptv); however, daytime concentrations below the canopy are two-to-three times larger than those above. In the rural scenario, NO3 contributes up to 20 % of daytime oxidation of α-pinene below the canopy, and this contribution increases to around 40 % in the polluted cases. Oxidation of isoprene is almost entirely dominated by reaction with OH, as expected. The most significant first-generation RONO2 formation mechanism varies significantly between scenarios and by canopy location. Nonetheless, in every scenario, daytime production of first-generation RONO2 through NO3 + α-pinene is more significant below the canopy than above. While SOA mass loadings are moderate (2 μg m−3 or less), total SOA production is consistently enhanced below the canopy, due to the combined effects of elevated isoprene and reduced NO concentrations. Furthermore, below the canopy, the total amount of RONO2 SOA produced through NO3 oxidation of α-pinene during the daytime (10:00–18:00), while small in absolute terms, is more than twice as large as the amount produced above the canopy during that time period in every scenario. In the rural ambient case, a minimum of 74 % of α-pinene RONO2 SOA is formed solely from initial oxidation by NO3. The relative abundances of HO2 and NO are shown to substantially impact both total SOA production and RONO2 SOA composition. The results presented emphasize the need for more detailed studies regarding the influence of NO3 throughout forest canopies in different environments.